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Cleavage of Sn−C and S−Calkyl Bonds on an Organotin Scaffold: Synthesis and Characterization of a Novel Organotin-Sulfite Cluster Bearing Methyltin- and Dimethyltin Fragments

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posted on 17.05.2010 by Ravi Shankar, Archana Jain, Gabriele Kociok-Köhn, Mary F. Mahon, Kieran C. Molloy
Hydrolysis of the mixed-ligand dimethyltin(ethoxy)ethanesulfonate, [Me2Sn(OEt)(OSO2Et)]n (1a) in moist hexane proceeds via disproportionation and partial cleavage of Sn−C and S−C bonds to afford a novel oxo-/hydroxo- organotin cluster of the composition [(Me2Sn)(MeSn)4(OSO2Et)2(OH)4(O)2(SO3)2] (1) bearing both mono- and dimethyltin fragments and in situ generated sulfite (SO32−) anion in the structural framework. On the other hand, similar reactions with analogous mixed ligand diorganotin precursors, [R2Sn(OR1)(OSO2R1)]n (R = n-Bu, R1 = Et (2a); R = Et, R1 = Me (3a)), result in the formation of tetranuclear diorganotin clusters, [{(n-Bu2Sn)2(OH)(OSO2Et)}O]2 (2) and [(Et2Sn)4(OH)(O)2(OSO2Me)3] (3), respectively. The activation of the Sn−C or S−C bond is not observed in these cases. These findings provide a preliminary insight into the unusual reactivity of 1a under hydrolytic conditions.